Hyperbranched amphiphilic polymeric additives and polymer compositions with increased surface energy

ABSTRACT

The surface energy of polymeric substrates is increased by the application or incorporation of novel amphiphilic block copolymers. The block copolymer additives comprise a linear hydrophilic polymer or oligomer and a random hyperbranched polymer or oligomer and is completely or partially terminated with lipophilic end groups. The polymeric articles or constructions which benefit from the application or incorporation of the amphiphilic block copolymers in the areas of anti-fog, dissipation of static electricity, paintability, dyeability, printability, wicking of moisture, adhesion and polymer compatibility include carpet fibers, composite fibers, agricultural films, nonwoven coverstock, exterior automotive bumper fascia, packaging, hygienic products, incompatible polymer blends, laminated articles and eyewear.

[0001] This application claims the benefit under 35 USC 119(e) of U.S.Provisional Application Serial No. 60/181,332 filed on Feb. 9,2000.

[0002] The present invention relates to novel asymmetric hyperbranchedcopolymers, a process for their preparation, and to their use as polymeradditives that migrate to the surface of a polymer and have beneficialeffects on the surface properties of the polymer.

[0003] Random hyperbranched polymers are known. Hyperbranched polymersare obtained from the random polymerization of monomers in the presenceof at least one polyfunctional monomer capable of introducing branching.Such a synthetic scheme is shown by Hawker and Devonport in “Step-GrowthPolymers for High-Performance Materials: New Synthetic Methods,”Hedrick, J. L. and Labadie, J. W., Eds., Am. Chem. Soc., Washington,D.C., 1996, pp. 191-193. Hult, et al., in “Advances in Polymer Science,”Vol. 143 (1999), Roovers, J., Ed., Springer, New York, pp. 1-34, presenta review of hyperbranched polymers.

[0004] U.S. Pat. No. 3,441,953 teaches that discrete esters of certainhindered dihydroxycarboxylic acids possess desirable properties andwhich may be used as textile softeners, lubricants, wetting andrewetting agents and textile assistants and which impart properties suchas improved softness, scorch resistance, wettability and rewettability,static control, lubricity, tensile and tear strengths and sewability totextile materials. An example is given where polyethylene glycol (PEG)is reacted with dimethylolpropionic acid(2,2-bis(hydroxymethyl)propionic acid or BMPA) to form a PEG monoesterof BMPA. This diol-ester is subsequently reacted with a tallow fattyacid to form the tallow fatty acid diester. In fact, it is believed thatin the first step that a discrete PEG-BMPA monoester is not formed butthat some hyperbranching must have occurred, resulting in ahyperbranched polyester.

[0005] Functionalization or end-capping of hyperbranched polymers withvarious groups is known.

[0006] WO 97/23538 and WO97/23539 disclose highly branched epoxidefunctional and alkenyl functional polyesters respectively. The polyesteris prepared by self-condensing a di, tri, or polyhydroxy functionalmonocarboxylic acid monomer and which polyester contains at least onecarboxyl group and multi hydroxyl groups. The polyester is reacted withan epoxide containing compound such as epichlorohydrin or a compoundcontaining an oxidizable unsaturation to introduce the epoxidefunctionality. Likewise, it is reacted with a compound containingallylic or acrylic groups to introduce the alkenyl functionality.

[0007] U.S. Pat. No. 3,669,939 discloses highly branchedself-condensates of polyhydroxymonocarboxylic acids, for exampledimethylolpropionic acid. Monocarboxylic acids may be present in thecondensation reaction. The resulting resins are useful in coatingcompositions.

[0008] U.S. Pat. No. 5,136,014 discloses hyperbranched polyesterpolymers and copolymers that may be chemically capped, crosslinked, orcopolymerized with diols or diicarboxylic acids. Suitable capping agentsinclude anhydrides, acyl chlorides, isocyanates andbenzylisothiocyanate.

[0009] Schmaljohann, et al., Polymeric Materials Science andEngineering, 77 (1997), p. 173, discloses that hyperbranched aromaticpolyesters and a hyperbranched polyester based on self-condensation of2,2-bis(hydroxymethyl)propionic acid may be functionalized with alkylacid chlorides of 2 to 18 carbon atoms, resulting in hyperbranchedpolyesters with an amphiphilic character.

[0010] Highly branched dendritic polymers are well known, as discussedfor example in “Polymeric Materials Encyclopedia,” Vol. 5 (1996), J. C.Salamone, Ed., CRC Press, New York, pp. 3049-3053. Dendritic polymershave a non-linear architecture and are intrinsically globular in shape.Discrete, stepwise synthetic methods are used to prepare highly branchedpure compounds, or dendrimers. As discussed by Hawker and Devonport in“Step-Growth Polymers for High-Performance Materials: New SyntheticMethods,” Hedrick, J. L. and Labadie, J. W., Eds., Am. Chem. Soc.,Washington, D.C., 1996, pp. 186-196, if the macromolecule has highlyregular branching which follows a strict geometric pattern, it is adendrimer. Dendrimers are typically monodisperse and are prepared in amulti-step approach with purifications at each stage.

[0011] The architecture of dendrimers is also discussed by Roovers andComanita in “Advances in Polymer Science,” Vol. 142 (1999), Roovers, J.,Ed., Springer, New York, pp. 179-228. Dendrimers consist of a coremolecule which defines the center of symmetry of the molecule, andbranching layers. Tomalia, et al., in Angew. Chem. Int. Ed. Eng., 29(1990), 138-175 disclose “starburst” dendrimers which consist of aninitiator core and branching groups.

[0012] Hyperbranched macromolecules result if the branching is randomand irregular and are therefore not monodisperse. There are significantamounts of failure sequences present in such hyperbranchedmacromolecules. As discussed by Malmstroem, et al., in Macromolecules,28 (1995), 1698-1703, a hyperbranched material contains a mixture oflinear and fully branched AB_(x) repeating units and has a degree ofbranching of less than unity. An ideal dendritic substance has a degreeof branching of unity.

[0013] It is taught in WO 99/00439 and WO 99/00440 that dendrimers arehighly symmetric, while similar macromolecules designated ashyperbranched and/or dendritic may to a certain degree hold anasymmetry, yet maintaining the highly branched tree-like structure.

[0014] U.S. Pat. No. 5,418,301 teaches polyester-based dendriticmacromolecules and their use as an alternative to conventional polyesteralkyd resins. The dendritic macromolecules are built from a symmetriccentral initiator molecule or initiator polymer and a monomeric chainextender having one carboxyl and two hydroxyl groups and is optionallycapped with a chain stopper. The macromolecules described therein areprepared in a stepwise fashion. The exemplified central initiatormolecules are ditrimethylolpropane, trimethylolpropane and ethoxylatedpentaerythritol. It is taught that the central initiator compound may bean alkoxylate polymer such as polyethylene glycol or polypropyleneglycol as well as polytetrahydrofuran.

[0015] U.S. Pat. No. 5,663,247 discloses dendritic or near dendritichyperbranched polyester-based macromolecules that comprise a centralnucleus, a monomeric or polymeric chain extender with at least threereactive sites and optionally a chain stopper. The central nucleus is anepoxide compound with at least one reactive epoxide group. The chainextender has at least one hydroxyl group and at least carboxyl or epoxygroup. The chain extender may be for example dimethylolpropionic acid.The examples given employ a stepwise preparation and employ as thenucleus a bisphenol A-diglycidyl ether and triglycidyl isocyanurate.

[0016] WO 96/13558 discloses a binder composition comprised of at leastone unsaturated monomer and at least one unsaturated polyester. Theunsaturated polyester is a dendritic or hyperbranched macromoleculecomprising a nucleus, a chain extender, and a chain stopper. The nucleushas at least one reactive hydroxyl or epoxide group. The chain extenderhas at least two reactive hydroxyl groups and at least one reactivecarboxyl group. The unsaturation in the polyester is introduced throughthe chain stopper. Stepwise methods are disclosed for the preparation ofthe polyesters. The exemplified polyesters are prepared from a nucleusof ethoxylated pentaerythritol.

[0017] WO 96/19537 discloses thermosetting materials such as compositeswith increased toughness with the incorporation of functionalizedpolyester dendritic or hyperbranched macromolecules in the thermosettingresin. The polyester macromolecules contain at least one primary orsecondary reactive site. The macromolecules are built from a nucleushaving at least one reactive epoxide or hydroxyl group, a chain extenderwith at least two reactive hydroxyl groups and at least one reactivecarboxyl group and a chain stopper. The reactive sites are introducedthrough the chain termination. The disclosed polyesters are prepared ina stepwise fashion. The exemplified polyesters are prepared from anucleus of pentaerythritol pentaethoxylate.

[0018] WO 97/49781 discloses a refrigeration working fluid comprising alubricant comprising at least one chain terminated dendritic orhyperbranched polyester macromolecule and a refrigerant. The polyestersare composed of a nucleus, a chain extender and a chain terminator. Thenucleus is a mono, di, tri, or polyfunctional alcohol or epoxide. Thechain extender is an hydroxy functional carboxylic acid and the chainterminator is a aliphatic carboxylic acid. The exemplified end-cappedhyperbranched polyesters are prepared in a stepwise fashion with anucleus of either neopentyl glycol or trimethylolpropane.

[0019] WO 97/45474 discloses thermoplastic polymers grafted withhyperbranched dendritic polyester macromolecules. The polyestermacromolecules consist of a nucleus, a chain extender and an optionalchain stopper. The nucleus has at least one reactive epoxide, hydroxyl,carboxyl or anhydride group. The chain extender has at least threereactive groups of which at least one is a hydroxyl group and at leastone is a carboxyl or anhydride group. The optional chain stopper may befor example an aliphatic carboxylic acid. The exemplified hyperbrancheddendritic polyesters are prepared according to a stepwise method withpentaerythritol pentaethoxylate as the nucleus.

[0020] WO 99/00439 discloses a process for the preparation ofhyperbranched dendritic polyester alcohols. The polyester alcohols(polymeric polyalcohols or polyols) have a symmetrical or nearsymmetrical highly branched structure. The polymeric polyalcohols arecomposed of an initiator molecule with one or more reactive groups andbranching chain extender molecules with three functional groups of whichtwo are hydroxyl groups and one is a group reactive to the initiatormolecule and/or hydroxyl groups. The two hydroxyl groups of thebranching chain extender are acetal protected during the addition.Deprotection and subsequent addition of another generation of acetalprotected chain extenders, etc., yields highly branched symmetricaldendrimers. WO 99/00440 discloses a similar process towards thepreparation of the same polymeric polyalcohols. A double stageconvergent synthesis is taught wherein the nucleus (initiator molecule)has one or more hydroxyl or epoxide groups. The branching chain extendermolecules have three functional groups of which two are hydroxyl groupsand one is a carboxyl group. The branching generations are preparedfirst from ketal protected chain extenders and a carboxyl protectedchain extender and deprotection/subsequent reaction steps. Afterdeprotecting the carboxyl group, the prepared branches are then coupledto the nucleus molecule. U.S. Pat. No. 5,041,516 discloses a stepwise“convergent” process for the preparation of polyaromatic ether andpolyamide dendrimers.

[0021] Linear polymer-dendrimer hybrids are known.

[0022] WO 93/21259 discloses dendritic macromolecules of specific shapessuch as barbells, kites, triblocks and knot shaped molecules and astepwise method for their preparation. Several of these specially shapedmacromolecules may be prepared by stepwise methods with theincorporation of a linear polymer such as a polyalkyl ether or apolystyrene. The dendritic polymer groups with unique reactive sites arepreferable prepared by the convergent growth method as disclosed in U.S.Pat. No. 5,041,516. All of the examples are performed with polyaromaticethers which are true dendrimers prepared by a convergent method asdisclosed in U.S. Pat. No. 5,041,516, J. Am. Chem. Soc. 112 (1990),7638-7647 and J. Chem. Soc. Perkin Trans. 1 (1991), 1059-1076. A broadrange of possible uses for the specially shaped compounds is envisioned,including surface modification and compatibilization. Roovers andComanita in “Advances in Polymer Science,” Vol. 142 (1999), Roovers, J.,Ed., Springer, New York, pp. 211-216 disclose similar hybridmacromolecules. The functional dendrimers are reacted with a linearpolymer to form the hybrids.

[0023] The use of polyalkylene oxide polymers towards effecting thesurface properties of a polymer is known.

[0024] Bergbreiter and Srinivas in Macromolecules 25 (1992), 636-643,disclose an “entrapment functionalization” approach towards modifyingthe surface of high-density polyethylene. Block cooligomers ofpolyethylene and poly(ethylene glycol) are prepared and intimately mixedwith virgin polyethylene. Analysis of polymer films prepared from thismixture showed that the poly(ethylene glycol) units ended up primarilyat the outermost layers of the film.

[0025] U.S. Pat. No. 5,217,573 teaches a method for removing laserprinter and xerographic toner, ink or the like from paper by alkalinewashing and flotation in the presence of a surfactant which has twolipophilic groups and one hydrophilic group. The lipophilic groups arederived from rosin acids and the hydrophilic group is derived frompolyethylene glycol.

[0026] U.S. Pat. No. 5,464,691 discloses the use of an amphiphilic resintowards modifying the surface energy of a polyolefin. The amphiphilicresins are composed of hydrocarbon sections and a polar section. Thehydrocarbon sections are derived from, for example, long-chain aliphaticcarboxylic acids and the polar section is derived from a telechelicdiol, for example polyethylene glycol.

[0027] U.S. Pat. No. 5,721,322 discloses a method for increasing thesurface activity of non-polar polymeric materials, in particularpolyolefins and polystyrenes, with the incorporation of a triblockcopolymer. The triblock copolymer has two sections compatible with thehost polymer, for example long-chain aliphatic groups. The centersection is derived from a polyepichlorohydrin telomer.

[0028] U.S. Pat. Nos. 5,240,985, 5,272,196, 5,281,438, 5,328,951disclose the use of an amphiphile towards increasing the surface energyof polyolefins. The amphiphile consists of a central hydrophiliccomponent and two lipophilic components. The hydrophilic component isderived from, for example, polyglycols and the lipophilic components arederived from, for example fatty acids.

[0029] It has now been found that certain amphiphilic block copolymeradditives are particularly effective towards increasing the surfaceenergy of polymeric substrates. The amphiphilic block copolymers arenovel and are comprised of a linear hydrophilic polymer, a hyperbranchedpolymer, and lipophilic end groups. The linear hydrophilic polymer isthe core or nucleus from which the branching is initiated. Thehyperbranched sections are random and irregular and contain failuresequences; they are not dendrimers.

DETAILED DISCLOSURE

[0030] Accordingly, a subject of this invention are novel (A)(B) and(B)(A)(B) amphiphilic block copolymers wherein

[0031] (A) is a linear hydrophilic polymer or oligomer,

[0032] (B) is a random hyperbranched polymer or oligomer, and

[0033] wherein said block copolymers are completely or partiallyterminated with lipophilic groups.

[0034] The hydrophilic polymer or oligomer component (A) is derived froma mono or di-functional telechelic polymer or oligomer and may itself bea homopolymer, block copolymer, random copolymer or alternatingcopolymer, or the corresponding oligomers.

[0035] Preferably, component (A) is derived from a homopolymer, blockcopolymer, random copolymer or alternating copolymer selected from thegroup consisting of poly(acrylate)s, poly(methacrylate)s, polyesters,poly(alkylene diol)s, poly(alkylene diol) monoalkyl ethers, poly(arylether)s, poly(vinyl alcohol)s, poly(acrylamide)s, poly(urea)s,poly(urethane)s, poly(methacrylamide)s, poly(ethylene imine)s,poly(vinyl ether)s, poly(vinyl ester)s, poly(epichlorohydrin),poly(glycidyl ether)s, poly(glycidyl ester)s, poly(carbonate)s,poly(thio ether)s, poly(thio ester)s, poly(alkyl sulfone)s, poly(arylsulfone)s, poly(amino acid)s, polyamides, epoxy resins, novolac resinsand quaternary ammonium polyacrylates and polyamines.

[0036] Quaternary ammonium polyacrylates are for examplepoly(diallyldimethylammonium chloride) (polyDADMAC),poly(dimethylaminoethylacrylate) (polyDMAEA) andpoly(diethylaminoethylacrylate) (polyDEAEA). Polyamides are for exampleNylon 6,6.

[0037] Also preferably, component (A) is derived from a linearhomopolymer with an {overscore (M)}n between 300 and 500,000 daltons.

[0038] Especially preferred as precursors for component (A) arepoly(acrylate), poly(methacrylate), poly(alkylene diol), poly(alkylenediol) monoalkyl ether, poly(aryl ether), poly(acrylamide),poly(methacrylamide), poly(ethylene imine), poly(vinyl ether) andpoly(vinyl ester) linear homopolymers with an {overscore (M)}n between300 and 5,000 daltons.

[0039] Most preferred as precursors for component (A) are thepoly(alkylene diol)s, for example poly(ethylene glycol)s andpoly(propylene glycol)s and the corresponding monoalkyl ethers.

[0040] Deserving of special mention as precursors for component (A) arethe monoalkyl ethers of poly(ethylene glycol) with an {overscore (M)}nbetween 300 and 5,000 daltons.

[0041] The reactive functional groups (a) of the telechelic polymer oroligomer precursor for (A), and through which the linkage with thehyperbranched component (B) is formed, are located on one or both endsof the polymer or oligomer chain.

[0042] The reactive functional group (a) may be, for example, —OH, —NHR,—NH₂, —SH, —SO₂H, —CO₂H, —COX, —CSOH, —COSH, —CS₂H, —NCO, epoxy, epoxyether, epoxy ester and X,

[0043] wherein X is Cl, Br or I and R is a linear or branched chainalkyl of 1 to 30 carbon atoms.

[0044] The random hyperbranched polymer or oligomer component (B) isderived from at least one multi-functional monomer which may undergoself-condensation to produce a highly branched structure. The monomer ormonomers have at least two different functional groups, (b) and (c),reactive with each other. The monomer or monomers contain one group (b)and two or more groups (c). Group (b) is also reactive with group (a),which reaction forms the linkage which is the focal point for thebranching structure.

[0045] The random hyperbranched polymer or oligomer component (B) mayitself be a homopolymer or a random copolymer or the correspondingoligomers.

[0046] Groups (b) and (c) have the same definition as (a) with theprovisos that (b) and (c) are not equivalent and that (b) is reactivewith (c).

[0047] Examples of multi-functional monomers useful in the presentinvention are those that have one carboxylic acid group (b) and twohydroxyl groups (c) or one carboxylic acid group (b) and two aminegroups (c).

[0048] The multi-functional monomers may be for exampledimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid, orBMPA), α,α-bis-(hydroxymethyl)-butyric acid,α,α,α-tris(hydroxymethyl)-acetic acid, α,α-bis(hydroxymethyl)-valericacid, α,α-bis(hydroxy)propionic acid, α-phenylcarboxylic acids having atleast two hydroxyl groups directly pendant to the phenyl ring (phenolichydroxyl groups) such as 3,5-dihydroxybenzoic acid or amino acids suchas serine, lysine, threonine, tyrosine, aspartic acid, glutamic acid andcysteine.

[0049] Above monomers wherein one or more of the hydroxyl groups arehydroxyalkyl substituted can possibly also be used as a monomer.

[0050] When component (B) is a random copolymer derived from twodifferent multi-functional monomers, the monomers may be for example twoof the monomers selected from above such as dimethylolpropionic acid andα,α-bis(hydroxymethyl)butyric acid.

[0051] Preferably, at least one of the multi-functional monomers isdimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid, orBMPA).

[0052] The terminal lipophilic groups may be for example straight orbranched chain alkyl of 1 to 100 carbon atoms, straight or branchedchain alkenyl of 1 to 100 carbon atoms, straight or branched chainalkynyl of 1 to 100 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,polycycloalkyl of 14 to 112 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenylalkenyl of 7 to 15 carbon atoms or phenylalkynyl of 7 to 15carbon atoms.

[0053] Preferably, the terminal lipophilic groups are straight orbranched chain alkyl, alkenyl or alkynyl, each of 14 to 22 carbon atoms.

[0054] Examples where the lipophilic groups are polycycloalkyl groupsare polynorbornene and hydrogenated polynorbornene.

[0055] The lipophilic groups are derived from the appropriate mono ordi-functional alkyl, alkenyl, alkynyl or cycloalkyl group with one ortwo reactive groups (d), wherein (d) is reactive with group (c) of themulti-functional monomer and/or the hyperbranched structure. Reactivegroup (d) has the same definition as groups (a), (b) and (c).

[0056] The terminal lipophilic groups may, for example, be derived frommono- or di-carboxylic acids, or where appropriate, reactive equivalentsof carboxylic acids such as anhydrides or acid chlorides. Examples ofsuitable precursors for the lipophilic groups are acetic acid, propionicacid, butyric acid, valeric acid, isobutyric acid, trimethylacetic acid,caproic acid, caprylic acid, heptanoic acid, capric acid, pelargonicacid, lauric acid, myristic acid, palmitic acid, stearic acid, behenicacid, lignoceric acid, ceratic acid, montanoic acid, isostearic acid,isononanoic acid, 2-ethylhexanoic acid, oleic acid, ricinoleic acid,linoleic acid, linolenic acid, erucic acid, soybean fatty acid, linseedfatty acid, dehydrated castor fatty acid, tall oil fatty acid, tung oilfatty acid, sunflower fatty acid, safflower fatty acid, acrylic acid,methacrylic acid, maleic anhydride, orthophthalic anhydride,terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacicacid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,succinic acid and polyolefin carboxylic acids.

[0057] Preferably, the lipophilic groups are derived from straight orbranched chain alkylcarboxylic acids of 14 to 22 carbon atoms.

[0058] Most preferably the lipophilic groups are derived from myristicacid, stearic acid, isostearic acid and behenic acid.

[0059] Further, the terminal lipophilic groups need not be equivalent,i.e., the copolymers of this invention may comprise terminal lipophilicgroups that are the same or different. The lipophilic groups then arederived from more than one mono or di-functional alkyl, alkenyl, alkynylor cycloalkyl groups as defined above.

[0060] Accordingly, the linkages formed between (A) and (B) and whichare focal points for the branching structure of the copolymer, and thelinkages formed between (B) and the terminal lipophilic groups may befor example —O—, —S—, —SO₂—, —CO₂—, —CONH—, —CONR—, —NH—, —NR—, —OCO₂—,—COS—, —CSO—, —CS₂—, —NHCONH—, —NHCSNH— and —OCH₂CHOHCH₂OCO—. Mostcommonly the linkages between (A) and (B) and between (B) and theterminal lipophilic groups are —OCO—.

[0061] As mentioned, the hyperbranched sections of the block copolymersof this invention are random and irregular and contain failuresequences. They contain linear and fully branched repeating units. Forexample, an (A)(B) copolymer of this invention, wherein component (A) isderived from poly(ethylene glycol) monomethyl ether (MPEG), component(B) is derived from dimethylolpropionic acid, the terminal lipophilicgroups are derived from an alkylcarboxylic acid (RCOOH) and the ratio ofdimethylolpropionic acid monomer units to MPEG is 5, will comprise amixture, among other perturbations, of the following branched and linearstructures:

[0062] It can be seen that the copolymer of the instant inventioncomprises a complex mixture where component (B) is fully branched,partially branched and linear.

[0063] Preferably, the ratio of monomer units of each component (B) tothe polymer or oligomer component (A) in the block copolymers of thisinvention is from about 1 to 1 to about 100 to 1. Most preferably, theratio is about 1 to 1 to about 10 to 1.

[0064] Another subject of this invention is the process for thepreparation of the novel block copolymers disclosed herein.

[0065] Surprisingly, it has been discovered that a one-pot, one-stepsynthesis, in which all three ingredients, the linear polymer oroligomer precursor for component (A), the multi-functional monomerprecursor or precursors for component (B) and the precursor orprecursors for the lipophilic terminating groups are added together atone time provides for effective conditions for the preparation of theblock copolymers of this invention.

[0066] Where the preferred precursors for preparation of the (A)(B)block copolymers of this invention are employed, for example wherecomponent (A) is derived from poly(ethylene glycol) monomethyl ether,component (B) is derived from dimethylolpropionic acid and the terminallipophilic groups are derived from stearic acid or isostearic acid, thereactions between the precursors, i.e. coupling reactions, areesterification reactions with the condensation of water. Thereforepreferably the process is an esterification process with thecondensation of water.

[0067] The process may also be employed where the precursors havereactive groups other than alcohols and carboxylic acids, for exampletransesterification reactions, or reactions involving amides, amines oracid chlorides.

[0068] If more than one monomer precursor for component (B) is employed,the different monomers may or may not be reactive with each other. Ifthey are reactive with each other, component (B) will be a randomcopolymer or cooligomer. If they are not reactive with each other,component (B) will be a homopolymer or homooligomer. In this instancemixtures of different (A)(B) and (B)(A)(B) block copolymers will result.In the case of (B)(A)(B) copolymers, the (B) groups may or may not beformed from the same monomer.

[0069] The reaction time may vary widely depending on conditions such astemperature, the nature of the reactants from which the components (A),(B) and the lipophilic groups are derived, and the stoichiometries ofthese reactants. In the preferred esterification process, the reactionis complete when the acid number during the course of the reactionlevels off, i.e. is no longer decreasing. Generally, a typical reactionis complete within the range of about 5 hours to about 30 hours.

[0070] In the preferred esterification process of the present inventionwater formed during the reaction is continuously removed by knownmethods such as azeotropic distillation, vacuum distillation, spargingwith an inert gas and the like.

[0071] In the preferred esterification process, an esterificationcatalyst is present in the reaction mixture at a level of about 0.1 toabout 2 percent by weight based on the entire reaction mixture.Preferably the esterification catalyst is present in the reactionmixture at a level of about 0.2 to about 1 percent by weight of theentire reaction mixture. The esterification catalyst may be any commonlyknown such catalyst, for example protic acids, Lewis acids, titanates,zinc catalysts and tin catalysts.

[0072] In the preferred one-pot esterification process of thisinvention, the reactions are performed in the temperature range fromabout 140° C. to about 220° C. Most preferably, the process is performedin the temperature range from about 160° C. to about 190° C.

[0073] Protic acid catalysts are for example naphthalenesulfonic acid,para-toluenesulfonic acid (p-TSA), methanesulfonic acid,trifluoromethanesulfonic acid, trifluoroacetic acid, sulfuric acid orphosphoric acid. A titanate catalyst is for example tetrabutyl titanate.A zinc catalyst is for example zinc powder or an organozinc compound. Atin catalyst is for example tin powder or an organotin compound.

[0074] In the present process, the molar ratio of the monomer precursoror precursors for component (B) to the reactive functional groups (a) ofthe precursor for component (A) is about 1:1 to about 100:1 and themolar ratio of the precursor or precursors for the lipophilic groups tothe monomer precursor or precursors for component (B) is about 1:5 toabout 2:1.

[0075] One outcome of the process of this invention is that theresulting amphiphilic block copolymers are random and irregular andcontain failure sequences, such as unreacted hydroxyl moieties in thecase of a hydroxyl-bearing monomer.

[0076] The novel block copolymers of this invention are especiallyeffective as additives that increase the surface energy of polymers,polymer blends and polymer composites (polymer substrates). It has beenfound that the linear hydrophilic polymer or oligomer portion of theblock copolymer migrates to the surface of the polymer substrate. Theterminal lipophilic groups, which are compatible with the polymersubstrate, act as “molecular anchors” and secure the additive to thesurface of the substrate. In some cases where the terminal lipophilicgroups of the copolymer additive are not equivalent, the affinity of theadditive for the substrate may be enhanced.

[0077] Accordingly, another subject of this invention are novelcompositions comprising

[0078] I.) one or more (A)(B) or (B)(A)(B) amphiphilic block copolymerswherein

[0079] (A) is a linear hydrophilic polymer or oligomer,

[0080] (B) is a random hyperbranched polymer or oligomer, and

[0081] wherein said block copolymers are completely or partiallyterminated with lipophilic groups, and

[0082] II.) a polymeric substrate,

[0083] wherein the surface energy or hydrophilicity of the polymericsubstrate is increased.

[0084] The polymeric substrate may be, for example, a polyolefin,polystyrene, polyester, polyamide, polyether, polysulfone,polycarbonate, polyurea, polyurethane and polysiloxane and any mixtureof these polymers.

[0085] Preferably the polymeric substrate is a polyolefin, for examplepolyethylene and polypropylene.

[0086] Examples for polyolefins are:

[0087] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), highdensity and high molecular weight polyethylene (HDPE-HMW), high densityand ultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE), (VLDPE) and (ULDPE).

[0088] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0089] i) radical polymerization (normally under high pressure and atelevated temperature).

[0090] ii) catalytic polymerization using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either p- or s-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerization medium. The catalysts can be used by themselves inthe polymerization or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0091] 2. Mixtures of the polymers mentioned under 1.), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0092] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/odene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethyene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0093] Preferred polyolefins are polyethylene or polypropylene and theircopolymers with mono- and diolefins.

[0094] Polystyrenes of the invention include styrene-butadienecopolymers and block copolymers, ABS, IPS and styrene-isoprenecopolymers and block copolymers.

[0095] In addition to component I.), the novel compositions may comprisefurther additives (stabilizers) such as, for example, the following:

[0096] 1. Antioxidants

[0097] 1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundec-1-yl)phenol,2,4-di-methyl-6-(1-methylheptadec-1-yl)phenol,2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof.

[0098] 1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6--tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

[0099] 1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

[0100] 1.4. Tocopherols, for example α-tocopherol, β-tocopherol,γ-tocopherol, δ-tocopherol and mixtures thereof (Vitamin E).

[0101] 1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

[0102] 1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadene,bis[2-(3'tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0103] 1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

[0104] 1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0105] 1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0106] 1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy benzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0107] 1.11 . Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0108] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0109] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0110] 1.14. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- orpolyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0111] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionicacid with mono- or polyhydric alcohols, e.g. with methanol, ethanol,octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0112] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0113] 1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugar® XL-1 supplied by Uniroyal).

[0114] 1.18. Ascorbic acid (vitamin C)

[0115] 1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-napthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclhexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylamincphenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyl diphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

[0116] 2. UV Absorbers and Light Stabilizers

[0117] 2.1. 2-(2-Hydroxyphenyl)benzotriazoles, for example2-(2-hydroxy-5-methylphenyl)-benzotriazole,2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole,2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole,2-(2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chloro-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-benzotriazole,2-(3-sec-butyl-5-tert-butyl-2-hydroxyphenyl)benzotriazole,2-(2-hydroxy-4-octyloxyphenyl)benzotriazole,2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole,2-(3,5-bis-(α,α-dimethylbenzyl)-2-hydroxyphenyl)benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3-tert-butyl-5-[2-(2-ethylhexyloxy)-carbonylethyl]-2-hydroxyphenyl)-5-chloro-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3-tert-butyl-5-[2-(2-ethylhexyloxy)carbonylethyl]-2-hydroxyphenyl)benzotriazole,2-(3-dodecyl-2-hydroxy-5-methylphenyl)benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3-tert-butyl-5-(2-methoxycarbonylethyl)-2-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂—] whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-(1,1,3,3-tetramethylbutyl)-phenyl]-benzotriazole;2-[2-hydroxy-3-(1,1,3,3-tetramethylbutyl)-5-(α,α-dimethylbenzyl)-phenyl]-benzotriazole.

[0118] 2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy,4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0119] 2.3. Esters of substituted and unsubstituted benzoic acids, asfor example 4-tertbutyl-phenyl salicylate, phenyl salicylate,octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

[0120] 2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate,isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate,methyl α-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0121] 2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

[0122] 2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethy14-piperidyl) sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl) succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxy-ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-piperidyl) succinate, linear orcyclic condensates ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperdyl)-hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-amino-propylamino)ethane, the condensateof2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane.,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane und epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylene-malonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,reaction product of maleic acid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

[0123] 2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

[0124] 2.8. 2-(2-Hydroxyphenyl)-1.3.5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dinethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,4,6-bis(2,4-dimethylphenyl)-2-[2-hydroxy-4-(2-hydroxy-3-nonyloxypropoxy)-5-(1-methyl-1-phenylethyl)phenyl]-1,3,5-triazine.

[0125] 3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazicle,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

[0126] 4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo[d,f][1,3,2]dioxaphosphepin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g][1,3,2]dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite.

[0127] Especially preferred are the following phosphites:

[0128] Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos® 168, CibaSpecialty Chemicals Corp.), tris(nonylphenyl) phosphite,

[0129] 5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0130] 6. Nitrones, for example N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

[0131] 7. Amine oxides, for example amine oxide derivatives as disclosedin U.S. Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide.

[0132] 8. Benzofuranones and indolinones, for example those disclosed inU.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No.5,175,312; U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643;DE-A4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0133] 9. Thiosynergists, for example dilauryl thiodipropionate ordistearyl thiiodipropionate.

[0134] 10. Peroxide scavengers, for example esters of β-thiodipropionicacid, for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

[0135] 11. Polyamide stabilizers, for example copper salts incombination with iodides and/or phosphorus compounds and salts ofdivalent manganese.

[0136] 12. Basic co-stabilizers, for example melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acids,for example, calcium stearate, zinc stearate, magnesium behenate,magnesium stearate, sodium ricinoleate and potassium palmitate, antimonypyrocatecholate or zinc pyrocatecholate.

[0137] 13. Nucleating agents, for example inorganic substances such astalcum, metal oxides such as titanium dioxide or magnesium oxide,phosphates, carbonates or sulfates of, preferably, alkaline earthmetals; organic compounds such as mono- or polycarboxylic acids and thesalts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid,diphenylacetic acid, sodium succinate or sodium benzoate; polymericcompounds such as ionic copolymers (ionomers).

[0138] 14. Fillers and reinforcing agents, for example calciumcarbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin,mica, barium sulfate, metal oxides and hydroxides, carbon black,graphite, wood flour and flours or fibers of other natural products,synthetic fibers.

[0139] 15. Other additives, for example plasticizers, lubricants,emulsifiers, pigments, dyes, optical brighteners, rheology additives,catalysts, flow-control agents, slip agents, crosslinking agents,crosslinking boosters, halogen scavengers, smoke inhibitors,flameproofing agents, antistatic agents, clarifying agents and blowingagents.

[0140] The amphiphilic block copolymer additives of component I.) areadvantageously present in the compositions of this invention from about0.1 to about 20 percent by weight based on the total weight ofcomponents I.) and II.), preferably from about 0.5 to about 5 percent byweight.

[0141] The amphiphilic block copolymer additives of this invention andoptional further additives may be applied to or incorporated in thepolymeric substrate by any known methods, e.g. by melt blending,solution blending, solution casting and adsorption from solution.

[0142] For example, component I.) and optional further additives may beincorporated in the polymeric substrate before or after molding or alsoby applying the dissolved or dispersed additive mixture to the polymericsubstrate, with or without subsequent evaporation of the solvent.Component I.) and optional further additives can also be added to thepolymeric substrate in the form of a masterbatch which contains thesecomponents in a concentration of, for example, about 2.5% to about 25%by weight.

[0143] For example, component I.), optional further additives and thepolymeric substrate may all be dissolved in a mutually compatiblesolvent wherein the concentration of polymer in the solvent ranges fromabout 5 to about 50% by weight of the solvent. The solution may then bedried at an appropriate temperature to produce a cast film containing ablend of polymer and the additive(s).

[0144] Alternatively, additive compounds of component I.) and optionalfurther additives are blended into a polymeric substrate by dissolvingthe additive(s) in a volatile solvent to provide a solution with anadditive concentration of about 5 to about 50% by weight. The solutionis then mixed with the polymer and the mixture is dried therebyproviding polymer particles which are substantially evenly coated withadditive(s). The coated polymer particles may then be fed to an extruderwherein the mixture is melt blended and extruded to produce an extrudatecontaining the polymeric substrate and additive(s).

[0145] If in a liquid form, the additives of component I.) may beapplied directly to polymer particles by stirring the polymer particlesin the liquid additive mixture until the additive mixture is evenlydispersed on the surface of the polymer particles. The polymer may thenbe fed to an extruder to produce an extrudate of polymer substratecontaining the additives.

[0146] The compositions of this invention may also be prepared bysubmitting the additives of component I.), optional further additivesand solid polymeric material to an extruder followed by melt blendingand extruding the molten mixture. Alternatively, the polymeric materialand additives may be melt blended in a thermostatted vessel where thecomponents are in molten form, followed by cooling of the mixture.

[0147] As the material cools, at least a portion of the additives ofcomponent I.) migrates to the surface of the polymeric substrate therebymodifying the surface properties thereof. The additives of component I.)are persistent in the polymeric substrate, and consequently the surfaceproperties are substantially permanently modified.

[0148] Component I.) and optional further additives can also be addedbefore or during the polymerization or before crosslinking.

[0149] Component I.) and optional further additives can be incorporatedinto the polymeric substrate in pure form or encapsulated in waxes, oilsor polymers.

[0150] Component I.) and optional further additives can also be sprayedor coated onto the polymeric substrate. It may be used to dilute otheradditives (for example the conventional additives indicated above) ortheir melts so that it can be sprayed or coated together with theseadditives onto the polymeric substrate. Addition by spraying during thedeactivation of the polymerization catalysts is particularlyadvantageous, it being possible to carry out spraying using, forexample, the steam used for deactivation.

[0151] In the case of spherically polymerized polyolefins it may, forexample, be advantageous to apply component I.) optionally together withother additives, by spraying.

[0152] Preferably, component I.) and optional further additives areincorporated into the polymeric substrate of component II.) by meltblending. As mentioned, under melt blending conditions, the blockcopolymer additives of component I.) migrate to the surface of theformed polymer substrate.

[0153] The polymeric compositions of this invention, which haveincreased surface energy or hydrophilicity, may exhibit improvedproperties in the areas of, for example, anti-fog, dissipation of staticelectricity, paintability, dyeability, printability, wicking ofmoisture, adhesion, compatibility with immiscible polymers,biocompatibility and biodegradibility.

[0154] The polymeric articles or constructions, which comprisecomponents I.) and II.), and which benefit from the application orincorporation of the amphiphilic block copolymers of this inventioninclude carpet fibers, composite fibers, agricultural films, nonwovencoverstock, exterior automotive bumper fascia, packaging, hygienicproducts, membranes such as semipermeable, dialysis and reverse osmosismembranes, incompatible polymer blends, laminated articles and eyewear.

[0155] The polymer blends that may be compatibilized with theincorporation of the amphiphilic block copolymers of this inventioninclude blends of polystyrene with polyesters, polystyrene withpolyamides, polyolefins with polyesters and polyolefins with polyamides.

[0156] The amphiphilic block copolymers of this invention are alsoeffective as rheology modifiers and dispersants for pigments andfillers. Articles that would benefit include solvent and water bornepaints.

[0157] Anti-fog properties are important in greenhouse applications. Agreenhouse is required to be closed during cold periods to contain heatto maintain a growing environment. With high humidity inside thegreenhouse, this creates a situation where water condenses on the insideof greenhouse roof or cover when the temperature of the roof or cover isreduced to the dew point or lower. A greenhouse film made from anolefinic polymer is hydrophobic and has low surface tension, whichcauses condensed water to coalesce into droplets. This unwantedcondition, where water condensate forms on the surface of the film asfree droplets, is known as “fogging.” Fogging prevents the transmissionof sunlight and may fall onto and damage the crop below. Compositions ofthe present invention have superior anti-fog properties. Anti-foggingproperties are also important in food overwrap (meat, vegetables, etc.)or other applications where a clear film with wettability or non-foggingis needed.

[0158] Hyperbranched polymers similar to those described herein, butwithout component (A) are also useful in the compositions of thisinvention. That is to say, a random hyperbranched polymer or oligomercomponent (B) as described above that is completely or partiallyterminated with lipophilic groups. Many of these hyperbranched polymersare novel. For example, the condensation reaction products ofdimethylolpropionic acid reacted with each of myristic acid, stearicacid, isostearic acid and behenic acid or mixtures thereof.

[0159] The following Examples illustrate the invention in more detail.They are not to be construed as limiting the instant invention in anymanner whatsoever. The invention is declared to cover all changes andmodifications of the specific examples which do not constitute departurefrom the spirit and scope of the invention.

EXAMPLE 1 Preparation of Amphiphilic Block Copolymers

[0160] A series of various amphiphilic block copolymers of the presentinvention are prepared according to the following general procedure.Comparative examples of linear amphiphilic polymers are prepared by thesame procedure with the exclusion of the multi-functional monomer. Thecomparative amphiphilic polymers are represented by numbers 1 and 2 ofTable 1 and are representative of state of the art nonionic surfactantsemployed for increasing the surface energy of polyolefins. Thecopolymers of the instant invention are represented by numbers 3-25. Thelinear hydrophilic polymer component (A) is derived from eitherpoly(ethylene glycol) monomethyl ether (MPEG) or poly(ethylene glycol)(PEG), and is represented in Table 1 by the symbol “A”. The molecularweight ({overscore (M)}n, daltons) of the hydrophilic polymer componentis given in Table 1. The random hyperbranched component(B) is derivedfrom dimethylolpropionic acid [2,2-bis(hydroxymethyl)propionic acid(BMPA)]. The lipophilic terminal groups are derived from thecorresponding long-chain alkylcarboxylic acid (“LCA” in Table 1). Theuse of stearic acid results in a C₁₇H₃₅ lipophilic group. The lastcolumn of Table 1 represents the ratio of components employed in thepreparation of the corresponding copolymer. The copolymers of theinstant invention comprise a mixture of structures as discussed supraand similar to compounds of formulae (1)-(4).

[0161] A reactor is charged with 89.9 g (316 mmol) of stearic acid, 31.8g (237 mmol) of BMPA, and 27.8 g (79 mmol) of MPEG₃₅₀ ({overscore (M)}n350 daltons, eq. wt. 349). Under a constant flow of nitrogen thetemperature of the solid mixture is increased to 110° C., at which pointthe solid mixture becomes a homogeneous colorless liquid. Stirring isinitiated and the reaction is allowed to purge for 30 min., and then 750mg (3.9 mmol) of p-toluenesulfonic acid are added. The reactiontemperature is increased to 160° C. Water of condensation immediatelycollects in a trap attached to the reactor. After 4 h, the reactiontemperature is increased between 180-190° C. Stirring at thistemperature is continued until the acid number shows little appreciabledecrease. Stirring is stopped and the hot liquid is poured into a glasscontainer and allowed to equilibrate to room temperature under ambientconditions. The structure of the (A)(B) block copolymer of the instantinvention is confirmed by ¹H, ¹³C FT-NMR spectroscopy, size exclusionchromatography (SEC), and differential scanning calorimetry (DSC).{overscore (Mn)}=1400, {overscore (M)}w/{overscore (M)}n=1.2, Tm=44° C.,acid number=29.0 mg KOH/g, hydroxyl number=31.5 mg KOH/g, yield isquantitative.

[0162] Likewise, the structures of the other (A)(B) or (B)(A)(B) blockcopolymers of the instant invention, as well as the comparative linearcopolymers, are confirmed by the same analytical techniques. TABLE 1Amphiphilic Copolymer Type LCA A, {overscore (M)}n LCA:A:B 1 linearC₃₃H₆₇CO₂H MPEG, 350 1:1:0 2 linear C₃₃H₆₇CO₂H PEG, 1000 2:1:0 3 (A) (B)C₁₃H₂₇CO₂H MPEG, 350 4:1:3 4 (A) (B) C₁₃H₂₇CO₂H MPEG, 550 4:1:3 5 (A)(B) C₁₃H₂₇CO₂H MPEG, 750 4:1:3 6 (A) (B) C₁₃H₂₇CO₂H MPEG, 1900 4:1:3 7(A) (B) C₁₃H₂₇CO₂H MPEG, 5000 4:1:3 8 (A) (B) C₁₇H₃₅CO₂H MPEG, 350 4:1:39 (A) (B) C₁₇H₃₅CO₂H MPEG, 550 4:1:3 10 (A) (B) C₁₇H₃₅CO₂H MPEG, 7504:1:3 11 (A) (B) C₁₇H₃₅CO₂H MPEG, 1900 4:1:3 12 (A) (B) C₁₇H₃₅CO₂H MPEG,5000 4:1:3 13 (A) (B) i-C₁₇H₃₅CO₂H MPEG, 350 4:1:3 14 (A) (B)i-C₁₇H₃₅CO₂H MPEG, 750 4:1:3 15 (A) (B) C₂₁H₄₃CO₂H MPEG, 350 4:1:3 16(A) (B) C₂₁H₄₃CO₂H MPEG, 550 4:1:3 17 (A) (B) C₂₁H₄₃CO₂H MPEG, 750 4:1:318 (A) (B) C₂₁H₄₃CO₂H MPEG, 1900 4:1:3 19 (A) (B) C₂₁H₄₃CO₂H MPEG, 50004:1:3 20 (B) (A) (B) C₃₃H₆₇CO₂H PEG, 1000 4:1:2

EXAMPLE 2 Preparation of Amphiphilic Block Copolymers

[0163] According to the general procedure described in Example 1, aseries of (A)(B) amphiphilic block copolymers of the present inventionare prepared. The linear hydrophilic polymer component is derived frompoly(ethylene glycol) monomethyl ether with an {overscore (M)}n of 350daltons and is represented by the symbol “P”. The random hyperbranchedcomponent is derived from dimethylolpropionic acid(2,2-bis(hydroxymethyl)propionic acid (BMPA)). The lipophilic terminalgroups are derived from isostearic acid as the long-chainalkylcarboxylic acid (“LCA”). Amphiphilic (A)(B) block copolymers of thepresent invention are prepared using the following ratios of LCA:P:BMPA:1:1:1, 2:1:1, 1:1:2, 2:1:2, 3:1:2, 1:1:3, 2:1:3, 3:1:3, 4:1:3, 1:1:4,2:1:4, 3:1:4, 4:1:4, 5:1:4, 1:1:5, 2:1:5, 3:1:5, 4:1:5, 5:1:5, 6:1:5,7:1:6, and 8:1:7.

EXAMPLE 3

[0164] According to the general procedure described in Example 1, aseries of (A)(B) amphiphilic block copolymers of the present inventionare prepared. Amphiphilic block copolymers are prepared using all of theratios of LCA:P:BMPA of Example 2 for each of the following combinationsof precursors for the lipophilic group and component (A). The randomhyperbranched component is derived from dimethylolpropionic acid(2,2-bis(hydroxymethyl)propionic acid (BMPA)).

[0165] a.) myristic acid, poly(ethylene glycol) monomethyl ether (MPEG)with an {overscore (M)}n of 350 daltons,

[0166] b.) myristic acid, MPEG with an {overscore (M)}n of 550 daltons,

[0167] c.) myristic acid, MPEG with an {overscore (M)}n of 750 daltons,

[0168] d.) stearic acid, MPEG with an {overscore (M)}n of 350 daltons,

[0169] e.) stearic acid, MPEG with an {overscore (M)}n of 550 daltons,

[0170] f.) stearic acid, MPEG with an {overscore (M)}n of 750 daltons,

[0171] g.) isostearic acid, MPEG with an {overscore (M)}n of 550daltons,

[0172] h.) isostearic acid, MPEG with an {overscore (M)}n of 750daltons,

[0173] i.) behenic acid, MPEG with an {overscore (M)}n of 350 daltons,

[0174] j.) behenic acid, MPEG with an {overscore (M)}n of 550 daltons,and

[0175] k.) behenic acid, MPEG with an {overscore (M)}n of 750 daltons.

EXAMPLE 4

[0176] According to the general procedure described in Example 1, aseries of (A)(B) amphiphilic block copolymers of the present inventionare prepared. Amphiphilic block copolymers are prepared using all of theratios of reactants of Example 2 for each of the combinations ofprecursors for the lipophilic group and component (A) as set forth inExample 3. The random hyperbranched component is derived from a 1:1mixture of dimethylolpropionic acid (2,2-bis(hydroxymethyl)propionicacid (BMPA)) and α,α-bis(hydroxymethyl)butyric acid.

EXAMPLE 5

[0177] According to the general procedure described in Example 1, aseries of (B)(A)(B) amphiphilic block copolymers of the presentinvention are prepared. The linear hydrophilic polymer component isderived from poly(ethylene glycol) with an {overscore (M)}n of 750daltons and is represented by the symbol “P”. The random hyperbranchedcomponent is derived from dimethylolpropionic acid(2,2-bis(hydroxymethyl)propionic acid (BMPA)). The lipophilic terminalgroups are derived from isostearic acid as the long-chainalkylcarboxylic acid (“LCA”). Amphiphilic (B)(A)(B) block copolymers ofthe present invention are prepared using the following ratios ofLCA:P:BMPA: 2:1:2, 4:1:2, 2:1:4, 4:1:4, 6:1:4, 2:1:6, 4:1:6, 6:1:6,8:1:6, 2:1:8, 4:1:8, 6:1:8, 8:1:8, 10:1:8, 2:1:10, 4:1:10, 6:1:10,8:1:10, 10:1:10, 12:1:10, 14:1:12, and 16:1:14.

EXAMPLE 6 Contact Angle Measurements in Compression Molded LDPE Plaques

[0178] Compression molded 10 mil plaques of copolymer additives of Table1 in low density polyethylene (Dow Chemical LDPE 640I) are prepared asfollows. The additives and substrate are initially blended by meltcompounding in a twin-screw extruder. Plaques of the blends are made bycompression molding against steel at 400° F.

[0179] Receding water contact angles of the compression molded plaquesare measured using a Kruss K12 dynamic contact angle tensiometer. Thismethod, often referred to as the Wilhelmy plat technique, measures theforce of wetting of a solid by a liquid (usually water) as it isinitially immersed and subsequently withdrawn. This wetting force isthen translated into receding (withdrawn) contact angles. It isgenerally accepted by those skilled in the art that receding contactangles are a measure of a materials' hydrophilic character.

[0180] The receding angles of the plaques are measured immediately aftercompression molding. They are rubbed five times with a water moistenedpaper towel and the receding angle is measured again. The plaques arestored at 70° F with a relative humidity of 30-40%. The receding anglesof the plaques are monitored over the course of 30 days. Comparison ofthe receding angles before and after rubbing gives a qualitative measureof the immediate persistence and relative modifying strength of theadditive, while the 30 day monitoring study provides insight as to theadditive's relative long-term persistence. The smaller the value of thereceding angle, the greater the surface energy of the LDPE plaque. TABLE2 Receding Contact Angles of LDPE Compression Molded Plaques Made withSteel Mold Surfaces Amphiphilic Initial Initial Aged (days) Copolymer %(w/w) Before Rub After Rub 5 10 30 None — 78.3 75.6 68.8 72.2 72.9 1 1.047.0 56.3 50.9 54.8 55.3 2 1.0 29.8 51.1 49.5 49.8 57.6 8 1.0 35.9 40.438.9 38.2 44.3 20  1.0 43.7 52.9 46.3 52.4 55.0 20  3.0 14.8 33.1 30.437.4 45.3

[0181] It can be seen that the amphiphilic block copolymers of thisinvention, represented by numbers 8 and 20 are effective towardsincreasing the surface energy of polyethylene. For comparison ofcompounds of the instant invention to nonionic surfactantsrepresentative of the state of the art, 20 should be compared to 2 and 8should be compared to 1. It can be seen that the compounds of theinstant invention increase the surface energy of LDPE to a greaterdegree than compounds representative of the state of the art and/or theyare more persistent in the substrate.

EXAMPLE 7 Contact Angle Measurements in LDPE Blown Films

[0182] When Example 6 is repeated in LDPE Blown Films, the compounds ofthe instant invention increase the surface energy of LDPE to a greaterdegree than compounds representative of the state of the art and/or theyare more persistent in the substrate as measured by receding, static oradvancing contact angles.

EXAMPLE 8 Polypropylene Fiber Dyeability

[0183] Fiber grade polypropylene, Montell PROFAX 6301, and theappropriate amount of additive are mixed on a TURBULA mixer for 15minutes. The blended mix is added to a SUPERIOR MPM single screw labextruder at 425, 450, 475 and 475° F., screw speed is 80 rpm. The moltenpolypropylene with additive exits a round die, is cooled in a watertrough and is fed into a CONAIR JETRO pelletizer. The compounded pelletsare fed into a HILLS LAB FIBER EXTRUDER with a 41 hole delta spinneretat 450, 475, 500 and 525° F. A constant pressure of 750 psi controls thescrew speed via a feed back loop. The feed, draw, and relax rolls are at175, 212 and 212° F., and are rotating at 120, 400 and 383 meters perminute. The fiber comes in contact with a 6% aqueous fiber finishsolution just before the feed roll. This solution is LUROL PP-4521 fromGoulston Indstries. A LEESONA winder at the end of the line collects thefiber onto a spool. The final denier per filament is 15. The collectedfiber is removed from the spool and is knitted into a sock with a LAWSONHEMPHILL FAK sampler knitter.

[0184] Solutions of dyes are prepared at 1.0 g/L in distilled water inseparate containers. For disperse dyes this is done by heating water to145-185° F., then adding water to the dye. The solutions of the aciddyes are made by heating water to 185-212° F. The solutions of theleveler, lubricant and pH control chemicals are made at room temperatureat a 10% w/w level.

[0185] A ROACHES programmable dye bath is set to the followingconditions:

[0186] Disperse dye for PP: Temperature rise of 3.5° C. per minute to98° C. with a hold time of 60 minutes at 98° C. then a cool down atmaximum cooling of 5.5° C. per minute.

[0187] Acid dye for PP: Temperature rise of 3.5° C. per minute to 98° C.with a hold time of 30 minutes at 98° C. then a cool down at maximumcooling of 5.5° C. per minute.

[0188] The appropriate amounts of the solutions (see Dye SolutionsTable) are added to a steel 500 mL cylinder based on a 5.0 g weight ofsock. The sock is identified with a laundry tag and is placed in thecylinder. The cylinder is filled with distilled water. The pH is checkedand should be 4-5 for disperse dyeing and 6-6.5 for acid dyeing. Finallythe cylinders are sealed and placed into the dye bath and the cycle isstarted. After the dye cycle is completed, the socks are removed fromthe cylinders and are rinsed with tap water. The excess water is removedfrom the socks via a centrifuge and are dried in a forced air oven at212° F. for 15 minutes.

[0189] Lightness and darkness (L) of the socks are measured on aDatacolor Spectrophotometer SF600. L is a measure of light and dark on ascale of 0 (dark) to 100 (light). Instrument conditions are CIE lab,D65, 10 deg, SCI, SAV, UV400-700. Results are found in Table 2. A lowerL value indicates improved dyeability. Dye Solutions Disperse Dye %Weight on Fiber Yellow K-GL 0.5 Red K-BB 0.5 Blue K-RB 1.0 UNIVADINE DIF2.0 CIBAFLUID UA 1.0 Acetic Acid 0.5

[0190] Disperse Dyeability Formulation LCA A, Mn L value A 54 Bi-C₁₇H₃₅CO₂H MPEG 750 21 C C₂₁H₄₃CO₂H MPEG 350 22 D C₂₁H₄₃CO₂H MPEG 190030

[0191] Formulation A contains no additive. Formulation B contains 5% byweight amphiphilic copolymer 14 of Example 1 based on the weight ofpolypropylene. C contains 5% by weight copolymer 15 of Example 1. Dcontains 5% by weight copolymer 18 of Example 1.

[0192] Formulations B, C, and D, containing additives of the presentinvention, impart improved dyeability to polypropylene socks compared tosocks containing no additive.

[0193] The crocking test method determines the degree of color which maybe transferred from the surface of a dyed article to other surfaces byrubbing. Such dye transfer is undesirable. The test requires specificrubbing, via a crockmeter, with both a dry and a wet white test clothacross the dyed article. The cloths are then evaluated via the grayscale. The gray scale is a 5 unit scale (1-5@0.5 divisions), with 5representing negligible dye transfer.

[0194] To qualify as a successful additive to promote polypropylene (PP)dyeability, the sock containing the additive will dye to a dark shade aswould be expected of a polyester (PET) control, there should be no ornegligible dye transfer when being evaluated by the crocking test, andthere should be no loss of physical properties.

[0195] The socks containing the amphiphilic block copolymers of thepresent invention show excellent dyeability as evidenced by low L valuesand acceptable wet and dry crock values.

EXAMPLE 9 Anti-Fog Properties of LDPE Blown Films

[0196] Amphiphilic block copolymer additives 3-5, 8-10 and 14 of ExampleI are added to low density polyethylene having a melt index of 2.0dg/min. and a density of 0.922 g/mL at 10% by weight, based on theweight of polymer, and the mixture is blended in a Brabender. Thepolymer melt temperature is 150° to 170° C. The polymer mixtures arepelletized to give a masterbatch. Granules of the masterbatch aretumble-blended with granules of low density polyethylene at the weightratio of 1 to 9 (the resulting concentration of the anti-fogging agentin the low density polyethylene polymer is 10,000 ppm). A film with athickness of about 75 micrometers is produced on a tubular blown filmline at a melt temperature of about 210° C.

[0197] The anti-fogging test method tests the ability of the filmsurface to retain its anti-fogging property after exposure to moistureunder cold (4° C.) and hot (60° C.) temperature conditions.

[0198] For the cold-fog test, 200 mL of water is put in a 250 mL beakerand the test film is placed on the beaker so as to cover the entireopening. The beaker is then placed in a temperature controlled cabinetat 4° C. Anti-fog evaluations are done in predetermined time intervalsup to 7 days.

[0199] For the hot-fog test, 50 mL of water is put in a 250 mL beakerand the test film is placed on the beaker so as to cover the entireopening. The beaker is then placed in a bath containing water at 60° C.Anti-fog evaluations are done in predetermined time intervals up to 3hours.

[0200] Anti-fogging ratings are as follows:

[0201] High fogging: 1

[0202] Moderate fogging: 2

[0203] Fogged in patches: 3

[0204] Few large drops: 4

[0205] Clear, no drops: 5

[0206] Polyethylene film containing the amphiphilic block copolymeradditives of the present invention have superior anti-fogging propertiesrelative to films with no surfactant additive and with state-of-the-artadditives such as Atmer® 103.

What is claimed is:
 1. An (A)(B) or a (B)(A)(B) amphiphilic blockcopolymer wherein (A) is a linear hydrophilic polymer or oligomer, (B)is a random hyperbranched polymer or oligomer, and wherein said blockcopolymer is completely or partially terminated with lipophilic groups.2. An amphiphilic block copolymer according to claim 1 in whichcomponent (A) is derived from a mono or di-functional homopolymer, blockcopolymer, random copolymer or alternating copolymer selected from thegroup consisting of the poly(acrylate)s, poly(methacrylate)s,polyesters, poly(alkylene diol)s, poly(alkylene diol) monoalkyl ethers,poly(aryl ether)s, poly(vinyl alcohol)s, poly(acrylamide)s, poly(urea)s,poly(urethane)s, poly(methacrylamide)s, poly(ethylene imine)s,poly(vinyl ether)s, poly(vinyl ester)s, poly(epichlorohydrin),poly(glycidyl ether)s, poly(glycidyl ester)s, poly(carbonate)s,poly(thio ether)s, poly(thio ester)s, poly(alkyl sulfone)s, poly(arylsulfone)s, poly(amino acid)s, polyamides, epoxy resins, novolac resinsand quaternary ammonium polyacrylates and polyamines.
 3. An amphiphilicblock copolymer according to claim 2 in which component (A) is derivedfrom a linear homopolymer with an {overscore (M)}n between 300 and500,000 daltons.
 4. An amphiphilic block copolymer according to claim 2in which component (A) is derived from a linear homopolymer with an{overscore (M)}n between 300 and 5,000 daltons and which is selectedfrom the group consisting of the poly(acrylate)s, poly(methacrylate)s,poly(alkylene diol)s, poly(alkylene diol) monoalkyl ethers, poly(arylether)s, poly(acrylamide)s, poly(methacrylamide)s, poly(ethyleneimine)s, poly(vinyl ether)s and poly(vinyl ester)s.
 5. An amphiphilicblock copolymer according to claim 4 in which component (A) is derivedfrom the group consisting of poly(ethylene glycol)s, poly(propyleneglycol)s, poly(ethylene glycol) monoalkyl ethers and poly(propyleneglycol) monoalkyl ethers.
 6. An amphiphilic (A)(B) block copolymeraccording to claim S in which component (A) is derived from apoly(ethylene glycol) monoalkyl ether.
 7. An amphiphilic block copolymeraccording to claim 1 wherein hyperbranched component (B) is derived fromat least one multi-functional monomer wherein said monomer or monomershave one reactive group (b) and two or more reactive groups (c) andwherein reactive groups (b) and (c) are reactive with each other undercondensation conditions.
 8. An amphiphilic block copolymer according toclaim 7 wherein hyperbranched component (B) is a random copolymer orcooligomer derived from at least two different monomers.
 9. Anamphiphilic block copolymer according to claim 7 wherein hyperbranchedcomponent (B) is derived from at least one multi-functional monomerwherein said monomer or monomers have one group (b) and two groups (c)wherein (b) is a carboxylic acid group and (c) is a hydroxyl group. 10.An amphiphilic block copolymer according to claim 9 wherein one of saidmonomers is dimethylolpropionic acid.
 11. An amphiphilic block copolymeraccording to claim 8 wherein hyperbranched component (B) is derived fromdimethylolpropionic acid and α,α-bis(hydroxymethyl)butyric acid.
 12. Anamphiphilic block copolymer according to claim 7 wherein the ratio ofmonomer units of each component (B) to the polymer or oligomer component(A) is from about 1 to 1 to about 100 to
 1. 13. An amphiphilic blockcopolymer according to claim 1 in which the terminal lipophilic groupsare independently straight or branched chain alkyl of 1 to 100 carbonatoms, straight or branched chain alkenyl of 1 to 100 carbon atoms,straight or branched chain alkynyl of 1 to 100 carbon atoms, cycloalkylof 5 to 12 carbon atoms, polycycloalkyl of 14 to 112 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenylalkenyl of 7 to 15 carbonatoms or phenylalkynyl of 7 to 15 carbon atoms.
 14. An amphiphilic blockcopolymer according to claim 13 in which the terminal lipophilic groupsare independently straight or branched chain alkyl of 14 to 22 carbonatoms, straight or branched chain alkenyl of 14 to 22 carbon atoms orstraight or branched chain alkynyl of 14 to 22 carbon atoms.
 15. Anamphiphilic block copolymer according to claim 14 in which the terminallipophilic groups are derived from myristic acid, stearic acid,isostearic acid or behenic acid.
 16. An amphiphilic (A)(B) blockcopolymer according to claim 1 in which component (A) is derived frompoly(ethylene glycol) monomethyl ether which has a {overscore (M)}nbetween 300 and 5,000 daltons, component (B) is derived fromdimethylolpropionic acid or dimethylolpropionic acid andα,α-bis(hydroxymethyl)butyric acid and the terminal lipophilic groupsare derived from stearic acid or isostearic acid.
 17. A one-pot,one-step process for the preparation of (A)(B) or (B)(A)(B) amphiphilicblock copolymers wherein (A) is a linear hydrophilic polymer oroligomer, (B) is a random hyperbranched polymer or oligomer, and whereinsaid block copolymers are completely or partially terminated withlipophilic groups which comprises adding the precursor for component (A)containing one or two reactive functional groups (a), themulti-functional monomer precursor or precursors for component (B) andthe precursor or precursors for the lipophilic terminating groups to areaction vessel at one time and heating the mixture to form saidamphiphilic block copolymers.
 18. A process according to claim 17wherein at least two different monomer precursors for component (B) areadded to said reaction vessel.
 19. A process according to claim 17 whichis an esterification process in which para-toluenesulfonic acid is addedas a catalyst together with the precursors of the amphiphilic blockcopolymers.
 20. A process according to claim 17 in which the molar ratioof the monomer precursor or precursors for component (B) to the reactivefunctional groups (a) of the precursor for component (A) is about 1:1 toabout 100:1 and the molar ratio of the precursor or precursors for thelipophilic groups to the monomer precursor or precursors for component(3) is about 1:5 to about 2:1.
 21. A composition comprising I.) one ormore additives selected from the group consisting of (A)(B) and(B)(A)(B) amphiphilic block copolymers wherein (A) is a linearhydrophilic polymer or oligomer, (B) is a random hyperbranched polymeror oligomer, and wherein said block copolymers are completely orpartially terminated with lipophilic groups, and II.) a polymericsubstrate, wherein the surface energy or hydrophilicity of the polymericsubstrate is increased.
 22. A composition according to claim 21 in whichcomponent II.) is one or more polymers selected from the groupconsisting of polyolefins, polystyrenes, polyesters, polyamides,polyethers, polysulfones, polycarbonates, polyureas, polyurethanes andpolysiloxanes.
 23. A composition according to claim 21 in whichcomponent II.) is a polyolefin.
 24. A composition according to claim 21in which component (A) is derived from a mono or di-functionalhomopolymer, block copolymer, random copolymer or alternating copolymerselected from the group consisting of the poly(acrylate)s,poly(methacrylate)s, polyesters, poly(alkylene diol)s, poly(alkylenediol) monoalkyl ethers, poly(aryl ether)s, poly(vinyl alcohol)s,poly(acrylamide)s, poly(urea)s, poly(urethane)s, poly(methacrylamide)s,poly(ethylene imine)s, poly(vinyl ether)s, poly(vinyl esters),poly(epichlorohydrin), poly(glycidyl ether)s, poly(glycidyl ester)s,poly(carbonate)s, poly(thio ether)s, poly(thio ester)s, poly(alkylsulfone)s, poly(aryl sulfone)s, poly(amino acid)s, polyamides, epoxyresins, novolac resins and quaternary ammonium polyacrylates andpolyamines.
 25. A composition according to claim 24 in which component(A) is derived from a linear homopolymer with an {overscore (M)}nbetween 300 and 500,000 daltons.
 26. A composition according to claim 24in which component (A) is derived from a linear homopolymer with an{overscore (M)}n between 300 and 5,000 daltons and which is selectedfrom the group consisting of the poly(acrylate)s, poly(methacrylate)s,poly(alkylene diol)s, poly(alkylene diol) monoalkyl ethers, poly(arylether)s, poly(acrylamide)s, poly(methacrylamide)s, poly(ethyleneimine)s, poly(vinyl ether)s and poly(vinyl ester)s.
 27. A compositionaccording to claim 26 in which component (A) is derived from the groupconsisting of poly(ethylene glycol)s, poly(propylene glycol)s,poly(ethylene glycol) monoalkyl ethers and poly(propylene glycol)monoalkyl ethers.
 28. A composition according to claim 27 in whichcomponent I.) is an (A)(B) amphiphilic block copolymer in whichcomponent (A) is derived from a poly(ethylene glycol) monoalkyl ether.29. A composition according to claim 21 wherein hyperbranched component(B) is derived from at least one multi-functional monomer wherein saidmonomer or monomers have one reactive group (b) and two or more reactivegroups (c) and wherein reactive groups (b) and (c) are reactive witheach other under condensation conditions.
 30. An composition accordingto claim 29 wherein hyperbranched component (B) is a random copolymer orcooligomer derived from at least two different monomers.
 31. Acomposition according to claim 29 wherein hyperbranched component (B) isderived from at least one multi-functional monomer wherein said monomeror monomers have one group (b) and two groups (c) wherein (b) is acarboxylic acid group and (c) is a hydroxyl group.
 32. A compositionaccording to claim 31 wherein one of said monomers isdimethylolpropionic acid.
 33. A composition according to claim 21 inwhich the terminal lipophilic groups are independently straight orbranched chain alkyl of 1 to 100 carbon atoms, straight or branchedchain alkenyl of 1 to 100 carbon atoms, straight or branched chainalkynyl of 1 to 100 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,polycycloalkyl of 14 to 112 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenylalkenyl of 7 to 15 carbon atoms or phenylalkynyl of 7 to 15carbon atoms.
 34. A composition according to claim 33 in which theterminal lipophilic groups are independently straight or branched chainalkyl of 14 to 22 carbon atoms, straight or branched chain alkenyl of 14to 22 carbon atoms or straight or branched chain alkynyl of 14 to 22carbon atoms.
 35. A composition according to claim 34 in which theterminal lipophilic groups are derived from myristic acid, stearic acid,isostearic acid or behenic acid.
 36. A composition according to claim 21in which component I.) is an amphiphilic (A)(B) block copolymer in whichcomponent (A) is derived from poly(ethylene glycol) monomethyl etherwhich has a {overscore (M)}n between 300 and 5,000 daltons, component(B) is derived from dimethylolpropionic acid or dimethylolpropionic acidand α,α-bis(hydroxymethyl)butyric acid and the terminal lipophilicgroups are derived from stearic acid or isostearic acid, and whereincomponent II.) is a polyolefin.
 37. A composition according to claim 21wherein component I.) is about 0.1 to about 20 percent by weight basedon the total weight of components I.) and II.).
 38. A compositionaccording to clam 37 wherein component I.) is about 0.5 to about 5percent by weight based on the total weight of components I.) and II.).39. A composition according to claim 21 in which component I.) isincorporated into component II.) by melt blending.
 40. A compositionaccording to claim 21 which contains further additives selected from thegroup consisting of phenolic antioxidants, ultraviolet light absorbers,organic phosphorus compounds, hydroxylamines and benzofuranones.
 41. Acomposition according to claim 21 which is an agricultural or packagingfilm, an exterior automotive part, a nonwoven fabric or filtrationmedium, a semipermeable membrane, an implantable medical device or atextile fiber.
 42. A composition according to claim 21 which is asolvent or water-borne paint.
 43. A composition according to claim 21 inwhich the polymer substrate of component II.) is compatible blend of anon-polar polymer and an additional polymer containing amine orcarboxylic acid end groups.
 44. A composition according to claim 43wherein the additional polymer containing amine or carboxylic acid endgroups is a polyamide or polyester.
 45. A method of increasing thesurface energy or hydrophilicity of a polymeric material wherein one ormore amphiphilic block copolymers according to claim 1 is applied to orincorporated into said polymeric material.